Triple‐Decker Au₃–Ag–Au₃–Ag–Au₃ Ion Cluster Enclosed in a Self‐Assembled Cage

Abstract

Soft d 10 metal ions (M), such as Au I and Ag I , show metallophilicity and form M···M interactions despite their electrostatic repulsion. [1] Although there are many examples of onedimensional arrays of these metal ions both in solution and in the solid state, [2] three-dimensionally controlled ionic clusters of these metals have seldom been synthesized. [3] We recently prepared a [3 3] Au I 9 cluster, [4] which consists of three layers of planar Au I 3 complex 2 a, in the confined cavity of selfassembled cage 1 a (Figure 1). Here, we report that trinuclear Au I 3 complex 2 b takes up silver ions to form an unprecedented triple-decker ion cluster (Au 3 -Ag-Au 3 -Ag-Au 3 ) in the cage. There is only one example of a double-decker sandwich cluster, Au 3 -Ag-Au 3 , prepared by the co-crystallization of a Au I trinuclear complex with a silver ion. [5] However, this structure is only observable in the solid state, and higher or infinite multi-decker clusters have never been [*] T.

Compressed Corannulene in a Molecular Cage

“…[2] Thes ize and shape of the cavity are particularly important to bind substrates in ap redicted array or aggregation manner.B ox-shaped, pillared cages, such as 1,s how strong binding abilities towards flat organic molecules or metal complexes in programmed stacking modes. The compressed corannulene structures are unambiguously revealed by single-crystal X-ray analysis.…”

“…[2] Thes ize and shape of the cavity are particularly important to bind substrates in ap redicted array or aggregation manner.B ox-shaped, pillared cages, such as 1,s how strong binding abilities towards flat organic molecules or metal complexes in programmed stacking modes. [2] Thes ize and shape of the cavity are particularly important to bind substrates in ap redicted array or aggregation manner.B ox-shaped, pillared cages, such as 1,s how strong binding abilities towards flat organic molecules or metal complexes in programmed stacking modes.…”

“…[2] Thes ize and shape of the cavity are particularly important to bind substrates in ap redicted array or aggregation manner.B ox-shaped, pillared cages, such as 1,s how strong binding abilities towards flat organic molecules or metal complexes in programmed stacking modes. [1] Herein, we show that corannulenes (2), bowlshaped non-planar aromatic compounds, [3] adapt their shape to fit into the box-shaped cavity of pillared cage 1 (Figure 1). …”

Macroscopic Self‐Assembly Based on Complementary Interactions between Nucleobase Pairs

“…[2][3][4][5][6] This is an attractive recognition motif that has been used to construct highly intelligent materials. Many researchers in chemistry and materials science have developed intelligent self-assembly systems on a molecular scale, for example, DNA origami, [7][8][9] 3D nanostructures, [10][11][12] metal arrays, [13][14][15] and stimuli-responsive DNA. [16] However, how to construct well-defined self-assemblies on the macroscopic scale is still a big issue for scientists.…”

Direct X‐Ray Scattering Evidence for Metal–Metal Interactions in Solution at the Molecular Level

“…[1] An increasing number of examples have been reported in which the binding strength and nature of interconnected metal ions influence the structure and physical characteristics of the resulting materials.Metal-metal interactions,and in particular, argentophilic interactions, [2] are akeystone in numerous assemblies,including in host-guest systems, [2] nanoparticles, [3] and in conducting, [4] luminescent, [5] and/or framework materials. [6] Tr aditionally,m etallophilic contacts exhibiting short metal-metal distances have been characterized in the solid-state by Xray crystallographic studies.M ore importantly,t he interactions in solution have been probed by spectroscopic methods (such as IR, Raman, UV/Vis,NMR, and ESR spectroscopies) and computational techniques have also been important in the study of such contacts.…”